Reactions of halogen-substituted olefins with alkenes and alcohols

ABSTRACT

IN REACTIONS INVOLVING THE OXIDATION OF OLEFINS BY RHODIUM TRICHLORIDE IN ALCOHOL SOLUTIONS, VINYL HALIDES OR ALLYLIC HALIDES CAN BE INCORPORATED INTO THE SYSTEM TO REGENERATE THE CATALYST. THE PRODUCTS OF BOTH OXIDATION AND REGENERATION REACTIONS COMPRISE OLEFINS AND/OR ACETALS AND/OR DETONES, E.G. 1-METHOXY-1-PHENYL ETHANE, 1,1-DIMETHOXYETHANE WHICH ARE USEFUL FOR OCTANE IMPROVERS.

United States Patent O 3,784,646 REACTIONS OF HALOGEN-SUBSTITUTED OLE- FINS WITH ALKENES AND ALCOHOLS John M. Holovka, Albuquerque, N. Mex., and Edward Hurley, Littleton, Colo., assignors to Marathon Oil Company, Findlay, Ohio No Drawing. Filed Aug. 18, 1970, Ser. No. 64,813 Int. Cl. C07c 49/08 US. Cl. 260-593 e 12 Claims ABSTRACT OF THE DISCLOSURE In reactions involvin the oxidation of olefins by rhodium trichloride in alcohol solutions, vinyl halides or allylic halides can be incorporated into the system to regenerate the catalyst. The products of both oxidation and regeneration reactions comprise olefins and/or acetals and/or ketones, e-g. l-methoxy-l-phenyl ethane, 1,1-dimethoxyethane which are useful for octane improvers.

CROSS REFERENCES TO RELATED APPLICATIONS Ser. No. 12,439, now US. Pat. 3,718,701, filed Feb. 18, 1970, relates to the oxidation of organic compounds under conditions of homogeneous catalysis.

BACKGROUND OF THE INVENTION Description of the prior art Various prior art patents have taught oxidation of hydrocarbons to ketones and aldehydes, particularly oxidation of ethylene to acetaldehyde. These include US. 3,285,970 which uses a Group VIII metal salt catalyst and a CuCl +O catalyst regeneration system; US. 3,290,362 which uses palladium metal regenerated with oxygen; US. 3,277,159 which uses palladium metal regenerated with oxygen; U.S.S.R. 165,436 which uses palladium halide regenerated with copper halide and oxygen; U.S.S.R. 137,508 which uses palladium chloride regenerated with copper chloride and oxygen or benzoquinone and oxygen; German 1,145,600 which uses platinum iodide and carbon dioxide as catalysts.

SUMMARY OF THE INVENTION (1) General statement of the invention It has now been found that, in reactions involving the oxidation of olefins by RhCl in alcohol solution, vinyl halides (i.e. olefins having one or more halogens attached to a carbon atom bearing a double bond) or allylic halides (i.e. olefins having one or more halogens attached to a carbon atom which is itself attached to a carbon atom bearing a double bond) can be incorporated in the system to regenerate the catalyst. The system can be chosen so that the olefin oxidation product and the vinylic or allylic halide reduction product are the same. Exemplary of the general reaction types which can be conducted according to the present invention are the following reactions:

eis or trans 2 CH:-CH(OR)z 2 R'X 2 H 3,784,646 Patented Jan. 8, 1974 In the above examples (V-VIII) hydrogens may be replaced by R", R or R" except on the alcohols.

(2) Utility of the invention Dimethoxy ethane is used as an octane improver in gasoline and as a solvent in perfume (see The Merck Index, p. 4). Other products of the invention are useful solvents.

PREFERRED EMBODIMENTS OF THE INVENTION 1) Starting materials (5) Pressure Generally the reaction is conducted in a sealed vessel under autogenous pressure, although pressure may be supplied by external means and is not narrowly critical and q 5 preferably ranges from 0.01 to about 10,000, more pref- QH. erably from 1 to about 1000, and most preferably 1 to 4, about 50 atmospheres. n! r r c Time where R and R are as described above.

While not narrowly critical it is preferred that R, React1on time 1s not narrowly cr1t1cal and Wlll vary and un contain from up to about 20, more Pref with the reactants, temperature and catalyst employed, erably from up to about 12, and most preferably from up but 1s preferably from about 0.01 to about 50, and more to about 6 carbon atoms. The most Preferred group preferably from about 0.1 to about 24, and most prefis chloro. erably from about 0.5 to about 1.5 hours.

Particularly preferred olefins are: ethylene, propylene, (7) B t h or ntin ou b is styrene, etc.; particularly preferred organic halides are: both cisand trans-1,2-dichloroethylene and vinyl chlothe g f i presgnt mventblon i ride; particularly preferred alcohols are: methanol, eth- Sen 6 a a c fl course 6 Prac 3 on a continuous basis with continuous flows of starting anol, and propanol.

materials mto and withdrawal of products from the re- (2) Reaction media actor.

While not usually to be preferred, various conventional (8) Optional additives to the macho organic liquids can be employed as re c ou ed a i Additional catalysts and/or solvents, radical initiators, speclallzed 50103? as y fi ly Inert etc. may be employed to enhance the rate of reaction asnot to enter mto side reactions. and yield of products. Those skilled in the art will be (3) Catalyst familiar with such optional procedures.

The catalyst of the present invention is rhodium halide, Examples 1 -er od chloride, rhodium bromlde, or q g The reactions are carried out in a sealed combustion iodide, preferably 111 hydrated form for ease of solubility. t b equipped i h a magnetic i i b and i The Pmfeffed y 1S IhOdIPIH chlorlde- The ing a mixture of reactants and catalyst(s). The tube is imalyst W111 Preferably be Present amounts of from mersed in an oil bath, heated to the desired temperature, 0-00001 t0 about more Preferably 9001 to about and held for a period of time until reaction is essentially 0.05, and most preferably .001 to about 0.01 mole per complete. The products are identified by gas chromam e of orgapw hahde startmg matenal. tography. Alkyl halides and H 0 are the principal by- It IS a p y va le feature of the nventlon that products. While the following examples are illustrative the feductlon 0f the y} allyhc hahde 111 mm 8 of preferred embodiments of the invention, they are not erates the catalyst by reoxidation. ant t limit the invention in any way.

4 Temperature EXAMPLES 1-20 The homogeneous catalysis reaction is preferably con- In a 20 cc. sealed Fischer-Porter combustion tube ducted in the range of from about 0 to about 400, more equipped with a magnetic stirring bar, the tube being impreferably from about to about 250, and most prefmersed in an oil bath maintained at the temperature indierably from about to about 200 F. In general, the cated inTable I, there is reacted the components indicated temperature will depend upon the particular reactants 45 in Table I. Therefater, gas chromatography is used to and catalyst employed as well as the pressure of reaction. analyze the product obtained. The product and the yield, The temperature is preferably controlled so that the reincluding the molar distribution thereof, and conversion actants remain substantially in the liquid phase. is indicated in Table I:

Ex. Beau; Run Time, Temp, Conversion,

No.- type No; Reactants, M Catalyst, mM; hr. 0. percent Products, M

1.-;..; I 23667 Me0H-0.63,t-dichloro- RhCh.3Ha0-0.378 18 100 1,1-dimethoxyethane0.07,

ethylene-0.053, ethyleneacetaldehyde0.02 water- 250 p.s.l. 0.08, methylchlori e0.06,

2-butenes-0.006.

2222 I 23668 MeOH-0.64,dichloro RhCl;.3HzO-0.34 18 No reaction.-..::2

ethylene-0.052.

32:2: II 23669 MeOH-0.64,dichloro- RhChBHaO-O-M 20 100 47212222222 1,1-dimethoxyethane0.024,

ethylene-0.052, propyleneacetone-0.025, water-0.04, 100 p.s.l; methyleh1or1de0.02,

unknown-0.4.

4.-23 41854 DME 0.0ll,MeOH-0.62, RhCh.3H:O-0.15 13 100 2222222222 ME.-

ethylene-250 p.s.l.

5..== 41855 Me311110.62;l (l).00076, nucaamo-oae 4.5 100 222 2 DME.-

6110- .S. c 6..::: 41856 Bnq1g]n0ln60 -014, Me1OH RhOhBHzO-OBO 2.5 100 100 ..TDME 0.014,hydroqu1none.-

7....: HI 23675 MeOII-0.%05 3vlnylcl ;1orlde-:RhCh.3HzO0.34 19 100 -100 011101101, DME --0.047 methyl- 0.076. 50 MeOH. chloride-0.04.

8 232222 23676 MeOH-2.5, trlchloro- RhCh.3H30O-7 85 200 2: "22:. Dimethyl ether-trace,

ethylene-0.2, ethylenemethyl chloride-trace, 830 p.31.- gutenestrace, DME

9..::.. II 23677 MeOH0.63,styrene-0.048, RhClaHz0-03 88 100 -67 styrenmaz: l-methoxy-l-phenyl-ethanw t-dichl0roethy1ene0.092. 0.017, acetopheone0.003.

10.-.: II 23682 MeOH-0.388,styrene0.025, RhClaHaO-O-M 17 100 100 benzoqulnone, l-methoxy-l-phenylethane benzoquinone-QOOIB. 42 styrene. acetophenone-unknown;

11...: 23683 MeOH-0.76, tetrachloro- RhChHzO-(L29 16 100 3: No DME I butenes-trace,

ethylene-ethylene-250 methylchlorlde-trace, p.31. dlmethyl ether-trace.

12 I 23684 Me0H-0.63, t-dlehlorm Rich-0.66 48 100 2222222222 DME -trace.

gglayleniwfifl, ethylene- 13 I... I 23700A Cls-di hloroethylenHm, RuCh.3HzO-0.33 16 100 2222322222 D0.

Me0H0.64, ethylene- 250 p.s.i.-

TABLE-Continued Ex. Reac. Run Time, Tem Conversion, No. type No. Reactants, M Catalyst, mM. hr. percent Products, M

14..-" 1 23700-3 Cis-dichloroethylene0.047, BhCl .3Hz-0.27 16 100 79...; DME --0.074.'

gIESOHTOAO, ethylenep.s. 15 I 50110-11 Trans-dichloroethylene0.06, RuCh.3Hz-0.35 16 100 No reaction;

3/50 T041, ethylenep.s. 16 I 50110-3 MeOH-0.51, trans-dichlow RuCh.3HzO-0.39 16 100 D0.

2%1ylene-0.082,ethylenep.s. 17 I 50110-0 MeOH-OA7, trans-dichloro- OSCla.3Hr-0.28 16 100 D0.

;gl6ylenie-0.082, ethylene-- p.s. 18 I 50121-A MBOH-0A15, trans-dichloro- IrCl;.3HgO-0.26 16 100 2:11-32:22: DME -trace;

ggl6yle11le0.048, ethylenep.s. 19.-.: 50122 MeOH-0.567, 1,1-dichl0ro- RhCh.3HzO-0.34 100 N0 reaction;

g5tl8ylenie-0.068, ethyleuep.s. 20.-.: IV 50130 MODE-0.315 allyl chlorlde- RhCla.3H20-O.34 16 100 100.-:;:::;:::':. DME 0.073 propyleneo.os25, ethylene-250 p.s.i.

'Ihese comparative examples indicate that alpha-alpha-dihalogensubstituted olefins are not suitable starting materials for the present invention, or at best react very slowly.

1 These comparative examples indicate the criticality oi the use of rhodium halides.

EXAMPLE 21 The procedure, reactants, catalysts and amounts are repeated according to Example 1 except that an equimolar amount of RhBr -3H O is substituted for the of Example 1. The principal products are water, 1,1-dimethoxyethane and methyl chloride.

EXAMPLE 22 The procedure, reactants, catalysts and amounts are repeated according to Example 1, except that is substituted for trans-dichloro ethylene. The principal products are water, 1,1-dimethoxyethane, 2- and 3-pentanones, and methyl bromide.

EXAMPLE 24 The procedure, reactants, catalysts and amounts are repeated according to Example 1 except that CH;H

Lon CH:

(isopropyl alcohol) is substituted for MeOH. The principal products are water, 1,1-di(2-propoxy)ethane, and 2- chloropropane.

EXAMPLE 25 The procedure, reactants, catalysts and amounts are repeated according to Example 1 except that butene-2 is substituted for the ethylene. The principal products are water,- methylethyl ketone, 1,1-dimethoxyethane, and methylchloride.

(10) Modifications It should be understood that the invention is capable of a variety of modifications and variations which will be made apparent to those skilled in the art by a reading of the specification and which are to be included within the spirit of the claims appended hereto.

0.033, aeeta1dehyde-0.010, water-0.08, methylchloride-0.08.

Product in these examples was diethoxyethaue due to presence of the auxiliary ligands, DME and or? which alter the dimerization reaction which would occur in their absence.

- DME-l, l-dimethoxyethane.

What is claimed is:

1. In a process for the preparation of acetals or ketones by a liquid-phase oxidation of olefins in the presence of rhodium halide salts and alcohols, the improvement comprising adding to the reaction mixture organic halide selected from the group consisting of vinyl iodides, vinyl bromides, vinyl chlorides, allylic bromides, allylic iodides, and allylic chlorides to regenerate the rhodium halide, conducting the reaction at a temperature of from about 0 to about 400 F. and at a pressure of from 0.01 to about 10,000 atmospheres, and wherein the organic halide has the structure wherein R, and R", can be the same or different, R, R", can each be hydrogen, alkyl, aryl, cycloalkyl, or alkaryl and can contain up to about 20 carbon atoms and wherein X is selected from the group consisting of chloro, bromo, and iodo.

2. The process of claim 1 wherein the vinyl halide has the structure:

wherein R and R can be the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, and aralkyl and contain from 1 to about 20 carbon atoms, and wherein X is selected from the group consisting of chloro, bromo, and iodo.

3. The process of claim 1 wherein the allylic halide has the structure:

wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, and aralkyl and contains from 1 to about 20 carbon atoms, and wherein X is selected from the group consisting of chloro, bromo, and iodo.

4. The process of claim 1 wherein the rhodium halide is rhodium chloride.

5. The process of claim 2 wherein the alcohol has the structure:

n -b-on wherein R'" and R" can be the same or ditferent and are selected from the group consisting of hydrogen, alkyl,

7 aryl, alkaryl, and aralkyl and each contain up to about 20 carbon atoms.

6. The process of claim 1 wherein the process is conducted on a substantially continuous basis with substantially continuous addition of vinyl halides or allylic halides, olefin and alcohol and wherein the acetals or ketone products are substantially continuously removed from the reaction mixture.

7. The process of claim 1 wherein the olefin has the structure:

wherein R and R" can be the same or different and are selected from the group consisting of hydrogen, phenyl groups, cycloalkyl groups, linear or branched-chained alkyl groups having 12 or fewer carbon atoms.

8. The process of claim 2 wherein R is hydrogen.

9. The process of claim 5 wherein R" is hydrogen.

10. The process of claim 7 wherein R" is hydrogen. 11. The process of claim 2 wherein R and R" are both hydrogen.

12. The process of claim 5 wherein R, R, R", R'", 5 and R" are each hydrogen.

References Cited UNITED STATES PATENTS 10 3,277,157 10/1966 Schaeffer 260-497 A DANIEL D. HORWITZ, Primary Examiner US. Cl. X.R

15 2606l5 A, 615 AA, 604 AC, 652 R, 683 R, 592, 614

AA, 396 R; 252-429 UN TED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,784,646 Dated January 8, 1974 Inventor(s) I Holovka et 8.1

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, line 12: Deiete "CH CH(OR') R'X" and insert: '-'-CH3-CH (OR 2+R X--. Table 1, Ex. No. 11: 7 Delete "tetrachloroethylene" and insert -tetrachloroethylene-0.05--.

Claim 5, line v V Delete "2" and substitute therefor 26th day of November 1974.

Signed and sealed this (SEAL) AtteSt:

c MARSHALL- DANN McCOY M. GIBSON, 'JR.

' Couunissioner of Patents Attesting Officer USCOMM-DC 6O376-P69 u.s. covlnunrwr nmmuo omcr; Ins o-ace-au.

FORM PC4050 (1069) 

